US6946414B2 - Glass-ceramics, process for the their preparation and use - Google Patents

Glass-ceramics, process for the their preparation and use Download PDF

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Publication number
US6946414B2
US6946414B2 US10/333,514 US33351403A US6946414B2 US 6946414 B2 US6946414 B2 US 6946414B2 US 33351403 A US33351403 A US 33351403A US 6946414 B2 US6946414 B2 US 6946414B2
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United States
Prior art keywords
sio
zro
cao
glass
pbo
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Expired - Fee Related
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US10/333,514
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US20040048729A1 (en
Inventor
Marco Bitossi
Giovanni Baldi
Enrico Generali
Davide Settembre Blundo
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Colorobbia Italia SpA
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Colorobbia Italia SpA
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Assigned to COLOROBBIA ITALIA S.P.A. reassignment COLOROBBIA ITALIA S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BALDI, GIOVANNI, BITOSSI, MARCO, BLUNDO, DAVIDE SETTEMBRE, GENERALI, ENRICO
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C04B41/5023—Glass-ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes

Definitions

  • the present invention refers to glass-ceramic consisting of:
  • glass is an amorphous material obtained by melting crystalline compounds followed by cooling down of the melted mass.
  • glass-ceramics are vitreous systems that, when brought to a temperature T 1 higher then their glass transition temperature T g and lower then the melting temperature, present the formation of crystal nuclei (homogeneous or heterogeneous) with following crystal growth.
  • the known glass-ceramics are normally prepared by melting the starting materials into a fused mass which thereafter is cooled down by quenching giving vitreous amorphous scales, technically called frits, which are thereafter applied, possibly in combination with other additives, on the appropriate porous substrate (or are added to the other necessary compound in a ceramic body if porcelain stonewares are desired) and undergo the firing process during which a crystallisation of the vitreous phase takes place and the final wanted ceramic material is obtained.
  • the melted mass can be cooled down and then submitted to appropriate proliferative cycles which induce the crystallisation in bulk.
  • vitreous frits A very important property of the vitreous frits is their thermal expansion coefficient ( ⁇ ) since they must follow the expansion of the porous substrate to which they are applied during the firing step. This is especially true in the so called double fast firing, single-firing gres technologies for the productions of glazes and engobes.
  • the invention solves the above said problems thanks to new glass-ceramic having the composition reported above.
  • Preferred according to the invention are glass ceramics having the following composition:
  • M 2 O represents a mixture of Li 2 O, Na 2 O and K 2 O, the total quantities of the mixture being as above defined as percentage of the total weight of the glass ceramic mixture.
  • glass-ceramics according to the present invention have the compositions reported hereinafter:
  • compositions according to the invention are reported in the following Table.
  • the glass-ceramic according to the invention can be used as such, in order to obtain ceramics, or can be added to the materials usually employed for preparing porcelain stoneware or glazes.
  • the glass-ceramics according to the invention allows (thanks to their “in situ” crystallisation) to confer to glaze an exceptional opacization which results in an higher white index (WI) compared to that obtained with the normal opacifiers added to glass, moreover, thanks to the chemical stability and high mechanical resistance of the crystalline phase re-crystallised on the glaze surface, they confer to the substrate physico-chemical properties higher then those of the traditional glazes.
  • WI white index
  • the glass-ceramics according to the present invention can be prepared according to a process which is substantially similar to those already applied in the art for the preparation of this kind of products.
  • the starting materials are melted, submitted to quenching in order to obtain the amorphous frits or, alternatively, the vitreous mass is cooled down to room temperature, according to known techniques (rolling, casting, glassblowing etc.), and thereafter submitted to the usual proliferative cycles (annealing, nucleation and growth) which cause the relaxation of internal strengths and induce the ceramisation of the vitreous mass.
  • frits are ground in a mill to give a vitreous powder which thereafter is applied to the wanted substrate, possibly in combination with the other additives normally used for the production of glazes or porcelain stoneware, and the substrate is submitted to the usual step of firing in order to obtain the final ceramic product as desired.
  • the starting oxides are melted in tank furnaces for ceramic frits (also gas or electric kilns for glass production can be used) and the melting temperature is normally comprised between 1400-1500° C.
  • the cooling is obtained by using water or cold stainless iron cylinders; if the crystallisation in bulk is preferred the normal techniques known in the glass technology for this purposes are applied.
  • the grinding of the frits is performed using the known techniques (ball-mills, drum-mills, etc.) the final dimension of the powders are normally comprised between 5-50 microns (powders), 0.05-0.35 mm (frits grains) or 0.14-0.63 mm (pellets grains) according to the requirements of the following applications.
  • the powders or grains obtained through the grinding can be worked in the following steps (i.e. in the preparation of the final glazed and porcelain stoneware products) according to the techniques and the conditions normally used in such processes and well known to the man skilled in the art.
  • the glass-ceramics according to the invention can be added to the materials normally used for the production of porcelain stoneware; the adding of the glass-ceramics according to the invention allows the production of ceramics via the process normally used for the production of porcelain stoneware this resulting in an important saving of energy.
  • a glass-ceramic according to the invention is added to a traditional mixture of starting materials for the production of porcelain stoneware (for example: clays, (Na,K) feldspate, Na feldspate, feldspate sand) in the appropriate proportions.
  • the mixture is loaded in a Alsing ball-mill (continuous or discontinuous) and ground in the presence of water to give a slurry which is dried in an atomiser forming hollow grains.
  • the grains are shaped in the desired form by traditional pressing.
  • the tiles are dried and fired in a traditional furnace at 900°-1230° C. giving the final product.
  • the glass-ceramics powder cold be mixed with spray dried body inside a cylindrical chamber using rotating ploughshare-shaped tools to improve the sintering.
  • a glass-ceramic according to the invention and a starting material usually employed for the production of ceramic glazes are loaded in a Alsing ball-mill in the presence of water and ground to obtain a so called “glazes” which was applied by airbrush, threading die, bell or serigraphy on a traditional substrate, crude or biscuited, obtained by pressing of atomised or dry-ground powders.
  • the glaze, dried and/or granulated can be deposited on the substrate surface by falling and fixed on the surface with appropriate ligants.
  • the pulverised glaze is combined with the porcelain stoneware body, then deposited in the mould of the press.
  • the substrate is fired at 900°-1230° C. in a quick- or tunnel-furnace (continuous or discontinuous) giving the final product in which the glass-ceramic has induced a controlled crystallisation.
  • the glass-ceramics according to the invention can be used for the production of tiles, sanitary-wares, table-wares, bricks etc. using the common techniques known in the art.
  • the tiles are dried and fired in a traditional furnace at 900°-1230° C. giving the final product.
  • the obtained tiles are constituted of syntherised and crystallised materials and a residual vitreous phase as demonstrated by mineral and X-ray analysis of the tile surface.
  • the mixture is loaded in an Alsing ball-mill in the presence of water and ground to obtain a so called glaze which was applied by airbrush on a traditional substrate, crude, obtained by pressing the usual atomised ground powders.
  • the substrate is fired at 900°-1230° C. in a quick- or tunnel-furnace (continuous or discontinuous) giving the final product in which the glass-ceramic has induced a controlled crystallisaton.
  • the glaze tiles so obtained present a vitreous and crystallised part which confer to the product a very well defined microstructure as shown by SEM and X-rays diffractometry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
US10/333,514 2000-07-21 2001-07-18 Glass-ceramics, process for the their preparation and use Expired - Fee Related US6946414B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP00115736.1 2000-07-21
EP00115736 2000-07-21
PCT/EP2001/008298 WO2002008135A1 (en) 2000-07-21 2001-07-18 Glass-ceramics, process for their preparation and use

Publications (2)

Publication Number Publication Date
US20040048729A1 US20040048729A1 (en) 2004-03-11
US6946414B2 true US6946414B2 (en) 2005-09-20

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US (1) US6946414B2 (es)
EP (1) EP1315678A1 (es)
CN (1) CN1220646C (es)
AU (1) AU2001289684A1 (es)
BR (1) BR0112648A (es)
CZ (1) CZ2003197A3 (es)
HU (1) HUP0301627A3 (es)
MX (1) MXPA03000574A (es)
PL (1) PL358676A1 (es)
RU (1) RU2293071C2 (es)
WO (1) WO2002008135A1 (es)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050239627A1 (en) * 2003-07-14 2005-10-27 Matsushita Electric Indus. Co., Ltd. Glass for multilayer film filter and method for manufacturing the glass
US20090142568A1 (en) * 2007-11-29 2009-06-04 Matthew John Dejneka Glasses having improved toughness and scratch resistance
US9670088B2 (en) 2014-05-20 2017-06-06 Corning Incorporated Scratch resistant glass and method of making

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US20040202632A1 (en) * 2003-04-10 2004-10-14 Unilever Home & Personal Care Usa, Division Of Conocpo, Inc. Fragranced solid cosmetic compositions based on a starch delivery system
CN1309680C (zh) * 2003-07-09 2007-04-11 山东硅苑新材料科技股份有限公司 低温烧结复相耐磨陶瓷材料
KR101048099B1 (ko) 2004-12-31 2011-07-11 주식회사 케이씨씨 고강도, 고탄성율을 가지는 유리 장섬유 조성물과 이를이용하여 제조되는 복합체
US20070022671A1 (en) * 2005-07-28 2007-02-01 Plemmons Harold F Weather resistant structure
ES2332441B1 (es) * 2008-05-20 2011-02-09 Cosentino, S.A. Procedimiento para la fabricacion de un articulo de piedra aglomeradacon resistencia termica.
US8341976B2 (en) 2009-02-19 2013-01-01 Corning Incorporated Method of separating strengthened glass
CN102976794B (zh) * 2012-11-30 2014-07-02 华南理工大学 利用铝型材工业废渣制备陶瓷熔块的方法
CN103663964B (zh) * 2013-12-06 2017-01-04 辽宁红山玉科技有限公司 一种高硅玉石状微晶玻璃
CN103922712B (zh) * 2014-04-04 2015-09-23 佛山市三水宏源陶瓷企业有限公司 微晶晶玉石瓷砖一次烧成工艺
CN105152534A (zh) * 2015-09-01 2015-12-16 广西南宁智翠科技咨询有限公司 一种强韧化玻璃陶瓷及其制备方法
CN105110649A (zh) * 2015-09-01 2015-12-02 广西南宁智翠科技咨询有限公司 一种高强度耐冲击玻璃陶瓷及其制备方法
CN105776873B (zh) * 2016-05-17 2018-06-15 齐鲁工业大学 一种“熔融-冷却”法析晶的高结晶度透明微晶玻璃
CN106830682A (zh) * 2017-01-17 2017-06-13 四川新高峰瓷业有限公司 一种防滑陶瓷釉料、防滑大理石瓷砖及其制备方法
CN107117821A (zh) * 2017-06-30 2017-09-01 合肥利裕泰玻璃制品有限公司 一种高强度微晶玻璃及其制备方法
CN107417115B (zh) * 2017-07-17 2020-04-03 佛山市简一陶瓷有限公司 一种高硬度高耐磨釉料的制作方法
CN107898126A (zh) * 2017-11-29 2018-04-13 浙江大学 一种复合型除垢牙刷丝及其制备方法
CN108030228A (zh) * 2017-11-29 2018-05-15 浙江大学 一种除垢牙刷丝及其制备方法
CN108838825B (zh) * 2018-06-07 2020-07-17 佛山市东鹏陶瓷有限公司 一种施底釉砖坯及釉面光滑的瓷砖生产方法
CN109928639A (zh) * 2019-01-31 2019-06-25 无锡麦格拉斯新材料有限公司 一种用于金属表面防护的微晶玻璃复合材料及其制备方法

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US3368712A (en) 1960-07-05 1968-02-13 Ritter Pfaudler Corp Semicrystalline glass and method of applying the same to metallic bases
US3565644A (en) 1967-03-22 1971-02-23 Scm Corp Composition for glazing ceramic ware
FR2102426A5 (en) 1970-07-16 1972-04-07 Le T Acid resistant glass crystalline enamel
WO1999007651A1 (en) 1997-08-11 1999-02-18 Colorobbia Italia S.P.A. Glass-ceramics process for their preparation and use
US5944884A (en) 1996-03-12 1999-08-31 Jeneric/Pentron Incorporated Dental porcelain composition
EP1000588A2 (de) 1998-11-13 2000-05-17 Degussa-Hüls Aktiengesellschaft Keramische Dentalrestauration
US6174608B1 (en) * 1997-11-27 2001-01-16 Ferro (Italia) Srl Ceramic tile and glaze for use thereon

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3368712A (en) 1960-07-05 1968-02-13 Ritter Pfaudler Corp Semicrystalline glass and method of applying the same to metallic bases
US3565644A (en) 1967-03-22 1971-02-23 Scm Corp Composition for glazing ceramic ware
FR2102426A5 (en) 1970-07-16 1972-04-07 Le T Acid resistant glass crystalline enamel
US5944884A (en) 1996-03-12 1999-08-31 Jeneric/Pentron Incorporated Dental porcelain composition
WO1999007651A1 (en) 1997-08-11 1999-02-18 Colorobbia Italia S.P.A. Glass-ceramics process for their preparation and use
US6605554B1 (en) * 1997-08-11 2003-08-12 Colorobbia Italia S.P.A. Glass-ceramics process for their preparation and use
US6174608B1 (en) * 1997-11-27 2001-01-16 Ferro (Italia) Srl Ceramic tile and glaze for use thereon
EP1000588A2 (de) 1998-11-13 2000-05-17 Degussa-Hüls Aktiengesellschaft Keramische Dentalrestauration

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050239627A1 (en) * 2003-07-14 2005-10-27 Matsushita Electric Indus. Co., Ltd. Glass for multilayer film filter and method for manufacturing the glass
US7151063B2 (en) * 2003-07-14 2006-12-19 Matsushita Electric Industrial Co., Ltd. Glass for multilayer film filter and method for manufacturing the glass
US20090142568A1 (en) * 2007-11-29 2009-06-04 Matthew John Dejneka Glasses having improved toughness and scratch resistance
US8652978B2 (en) 2007-11-29 2014-02-18 Corning Incorporated Glasses having improved toughness and scratch resistance
US8969226B2 (en) 2007-11-29 2015-03-03 Corning Incorporated Glasses having improved toughness and scratch resistance
US9809487B2 (en) 2007-11-29 2017-11-07 Corning Incorporated Glasses having improved toughness and scratch resistance
US10364178B2 (en) 2007-11-29 2019-07-30 Corning Incorporated Glasses having improved toughness and scratch resistance
US10464839B2 (en) 2007-11-29 2019-11-05 Corning Incorporated Glasses having improved toughness and scratch resistance
US11370695B2 (en) 2007-11-29 2022-06-28 Corning Incorporated Glasses having improved toughness and scratch resistance
US9670088B2 (en) 2014-05-20 2017-06-06 Corning Incorporated Scratch resistant glass and method of making
US11034611B2 (en) 2014-05-20 2021-06-15 Corning Incorporated Scratch resistant glass and method of making

Also Published As

Publication number Publication date
EP1315678A1 (en) 2003-06-04
HUP0301627A3 (en) 2009-03-02
AU2001289684A1 (en) 2002-02-05
US20040048729A1 (en) 2004-03-11
CZ2003197A3 (en) 2004-03-17
RU2293071C2 (ru) 2007-02-10
MXPA03000574A (es) 2003-06-06
BR0112648A (pt) 2003-06-24
HUP0301627A2 (hu) 2003-08-28
PL358676A1 (en) 2004-08-09
CN1443144A (zh) 2003-09-17
WO2002008135A1 (en) 2002-01-31
CN1220646C (zh) 2005-09-28

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